Abstract
CO2 reduction has been pursued for decades as an effective way to produce useful fuels and to mitigate global warming at the same time. Methanol synthesis from CO2 hydrogenation over Cu-based catalysts plays an important role in the chemical and energy industries. However, fundamental questions regarding the reaction mechanism and key reaction intermediates of this process are still unclear. To address these issues, we studied the CO2 hydrogenation process using density functional theory (DFT) combined with van der Waals (vdW) force corrections, finding that the most effective pathway proceeds along the reaction series CO* → CHO* → CH2O* → CH2OH* → CH3OH* with the reactive intermediate CH2O*, which is consistent with experimental findings. Additionally, we find that water molecules play an inhibiting role in the reaction, while H bonds and vdW forces have an essential effect on the reaction mechanisms. These findings shed light on the reaction mechanism of CH3OH formation from CO2 hydrogenation and reveal the essence of H2O in this reaction, providing a useful basis for preceding studies.
Similar content being viewed by others
References
E.V. Kondratenko, G. Mul, J. Baltrusaitis, G.O. Larrazabal, J. Perez-Ramirez, Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes. Energy Environ. Sci. 6, 3112–3135 (2013)
K.C. Waugh, Methanol synthesis. Catal. Today 15, 51–75 (1992)
K.P. Kuhl, E.R. Cave, D.N. Abram, T.F. Jaramillo, New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy Environ. Sci. 5, 7050–7059 (2012)
F. Studt, I. Sharafutdinov, F. Abild-Pedersen, C.F. Elkjær, J.S. Hummelshøj, S. Dahl, I. Chorkendorff, J.K. Nørskov, Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol. Nat. Chem. 6, 320–324 (2014)
J. Graciani, K. Mudiyanselage, F. Xu, A.E. Baber, J. Evans, S.D. Senanayake, D.J. Stacchiola, P. Liu, J. Hrbek, J.F. Sanz, J.A. Rodriguez, Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2. Science 345, 546–550 (2014)
O. Martin, A.J. Martín, C. Mondelli, S. Mitchell, T.F. Segawa, R. Hauert, C. Drouilly, D. Curulla-Ferré, J. Pérez-Ramírez, Indium oxide as a superior catalyst for methanol synthesis by CO2 hydrogenation. Angew. Chem. Int. Ed. 55, 1–16 (2016)
E.E. Barton, D.M. Rampulla, A.B. Bocarsly, Selective solar-driven reduction of CO2 to methanol using a catalyzed p-GaP based photoelectrochemical cell. J. Am. Chem. Soc. 130, 6342–6344 (2008)
L.V. MacDougall, Methanol to fuels routes—the achievements and remaining problems. Catal. Today 8, 337–369 (1991)
L.K. Rihko-Struckmann, A. Peschel, R. Hanke-Rauschenbach, K. Sundmacher, Assessment of methanol synthesis utilizing exhaust CO2 for chemical storage of electrical energy. Ind. Eng. Chem. Res. 49, 11073–11078 (2010)
G.A. Olah, Beyond oil and gas: The methanol economy. Angew. Chem. Int. Ed. 44, 2636–2639 (2005)
J.D. Grunwaldt, A.M. Molenbroek, N.Y. Topsøe, H. Topsøe, B.S. Clausen, In situ investigations of structural changes in Cu/ZnO catalysts. J. Catal. 194, 452–460 (2000)
M. Muhler, E. Törnqvist, L.P. Nielsen, B.S. Clausen, H. Topsøe, On the role of adsorbed atomic oxygen and CO2 in copper based methanol synthesis catalysts. Catal. Lett. 25, 1–10 (1994)
P.L. Hansen, J.B. Wagner, S. Helveg, J.R. Rostrup-Nielsen, B.S. Clausen, H. Topsøe, Atom-resolved imaging of dynamic shape changes in supported copper nanocrystals. Science 295, 2053–2055 (2002)
X. Dong, H.-B. Zhang, G.-D. Lin, Y.-Z. Yuan, K.R. Tsai, Highly active CNT-promoted cu-ZnO-Al2O3 catalyst for methanol synthesis from H2/CO/CO2. Catal. Lett. 85, 237–246 (2003)
J.S. Lee, K.I. Moon, S.H. Lee, S.Y. Lee, Y.G. Kim, Modified Cu/ZnO/Al2O3 catalysts for methanol synthesis from CO2/H2 and CO/H2. Catal. Lett. 34, 93–99 (1995)
F. Liao, Y. Huang, J. Ge, W. Zheng, K. Tedsree, P. Collier, X. Hong, S.C. Tsang, Morphology-dependent interactions of ZnO with Cu nanoparticles at the materials’ interface in selective hydrogenation of CO2 to CH3OH. Angew. Chem. Int. Ed. 50, 2162–2165 (2011)
O.-S. Joo, K.-D. Jung, I. Moon, A.Y. Rozovskii, G.I. Lin, S.-H. Han, S.-J. Uhm, Carbon dioxide hydrogenation to form methanol via a reverse-water-gas-shift reaction (the CAMERE process). Ind. Eng. Chem. Res. 38, 1808–1812 (1999)
K.M.V. Bussche, G.F. Froment, A steady-state kinetic model for methanol synthesis and the water gas shift reaction on a commercial Cu/ZnO/Al2O3 catalyst. J. Catal. 161, 1–10 (1996)
E.L. Kunkes, F. Studt, F. Abild-Pedersen, R. Schlögl, M. Behrens, Hydrogenation of CO2 to methanol and CO on Cu/ZnO/Al2O3: Is there a common intermediate or not? J. Catal. 328, 43–48 (2015)
J. Yoshihara, C.T. Campbell, Methanol synthesis and reverse water–gas shift kinetics over Cu(110) model catalysts: structural sensitivity. J. Catal. 161, 776–782 (1996)
G.C. Chinchen, K.C. Waugh, D.A. Whan, The activity and state of the copper surface in methanol synthesis catalysts. Appl. Catal. 25, 101–107 (1986)
P.B. Rasmussen, M. Kazuta, I. Chorkendorff, Synthesis of methanol from a mixture of H2 and CO2 on Cu(100). Surf. Sci. 318, 267–280 (1994)
J. Nakamura, Y. Choi, T. Fujitani, On the issue of the active site and the role of ZnO in Cu/ZnO methanol synthesis catalysts. Top. Catal. 22, 277–285 (2003)
Y. Yang, J. Evans, J.A. Rodriguez, M.G. White, P. Liu, Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001). Phys. Chem. Chem. Phys. 12, 9909–9917 (2010)
M. Behrens, F. Studt, I. Kasatkin, S. Kühl, M. Hävecker, F. Abild-Pedersen, S. Zander, F. Girgsdies, P. Kurr, B.-L. Kniep, M. Tovar, R.W. Fischer, J.K. Nørskov, R. Schlögl, The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science 336, 893–897 (2012)
S. Kuld, M. Thorhauge, H. Falsig, C.F. Elkjær, S. Helveg, I. Chorkendorff, J. Sehested, Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis. Science 352, 969–974 (2016)
S.A. Kondrat, P.J. Smith, P.P. Wells, P.A. Chater, J.H. Carter, D.J. Morgan, E.M. Fiordaliso, J.B. Wagner, T.E. Davies, L. Lu, J.K. Bartley, S.H. Taylor, M.S. Spencer, C.J. Kiely, G.J. Kelly, C.W. Park, M.J. Rosseinsky, G.J. Hutchings, Stable amorphous georgeite as a precursor to a high-activity catalyst. Nature 531, 83–87 (2016)
R. van den Berg, G. Prieto, G. Korpershoek, L.I. van der Wal, A.J. van Bunningen, S. Lægsgaard-Jørgensen, P.E. de Jongh, K.P. de Jong, Structure sensitivity of Cu and CuZn catalysts relevant to industrial methanol synthesis. Nat. Commun. 7, 13057 (2016)
S. Kattel, P.J. Ramírez, J.G. Chen, J.A. Rodriguez, P. Liu, Active sites for CO2 hydrogenation to methanol on cu/ZnO catalysts. Science 355, 1296–1299 (2017)
W. Janse van Rensburg, M.A. Petersen, M.S. Datt, J.-A. den Berg, P. Helden, On the kinetic interpretation of DFT-derived energy profiles: Cu-catalyzed methanol synthesis. Catal. Lett. 145, 559–568 (2014)
G.C. Chinchen, P.J. Denny, D.G. Parker, M.S. Spencer, D.A. Whan, Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts: use of 14C-labelled reactants. Appl. Catal. 30, 333–338 (1987)
Y. Yang, C.A. Mims, D.H. Mei, C.H.F. Peden, C.T. Campbell, Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures: The source of C in methanol and the role of water. J. Catal. 298, 10–17 (2013)
E.E. Ortelli, J.M. Weigel, A. Wokaun, Methanol synthesis pathway over Cu/ZrO2 catalysts: a time-resolved D RIFT 13C-labelling experiment. Catal. Lett. 54, 41–48 (1998)
J. Ye, C. Liu, D. Mei, Q. Ge, Active oxygen vacancy site for methanol synthesis from CO2 hydrogenation on In2O3(110): a DFT study. ACS Catal. 3, 1296–1306 (2013)
J. Kiss, J. Frenzel, N.N. Nair, B. Meyer, D. Marx, Methanol synthesis on ZnO(0001). III. Free energy landscapes, reaction pathways, and mechanistic insights. J. Chem. Phys. 134, 064710 (2011)
Y. Yang, M.G. White, P. Liu, Theoretical study of methanol synthesis from CO2 yydrogenation on metal-doped Cu(111) surfaces. J. Phys. Chem. C 116, 248–256 (2012)
Y.-F. Zhao, R. Rousseau, J. Li, D. Mei, Theoretical study of syngas hydrogenation to methanol on the polar Zn-terminated ZnO(0001) surface. J. Phys. Chem. C 116, 15952–15961 (2012)
C. Liu, P. Liu, Mechanistic study of methanol synthesis from CO2 and H2 on a modified model Mo6S8 cluster. ACS Catal. 5, 1004–1012 (2015)
F. Studt, M. Behrens, E.L. Kunkes, N. Thomas, S. Zander, A. Tarasov, J. Schumann, E. Frei, J.B. Varley, F. Abild-Pedersen, J.K. Nørskov, R. Schlögl, The mechanism of CO and CO2 hydrogenation to methanol over Cu-based catalysts. ChemCatChem 7, 1105–1111 (2015)
F. Studt, F. Abild-Pedersen, J.B. Varley, J.K. Nørskov, CO and CO2 hydrogenation to methanol calculated using the BEEF-vdW functional. Catal. Lett. 143, 71–73 (2012)
Q.-L. Tang, Q.-J. Hong, Z.-P. Liu, CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo. J. Catal. 263, 114–122 (2009)
L.C. Grabow, M. Mavrikakis, Mechanism of methanol synthesis on Cu through CO2 and CO hydrogenation. ACS Catal. 1, 365–384 (2011)
A.J. Medford, J. Sehested, J. Rossmeisl, I. Chorkendorff, F. Studt, J.K. Nørskov, P.G. Moses, Thermochemistry and micro-kinetic analysis of methanol synthesis on ZnO (0001). J. Catal. 309, 397–407 (2014)
Y.-F. Zhao, Y. Yang, C. Mims, C.H.F. Peden, J. Li, D. Mei, Insight into methanol synthesis from CO2 hydrogenation on Cu(1 1 1): Complex reaction network and the effects of H2O. J. Catal. 281, 199–211 (2011)
X. Nie, W. Luo, M.J. Janik, A. Asthagiri, Reaction mechanisms of CO2 electrochemical reduction on Cu(111) determined with density functional theory. J. Catal. 312, 108–122 (2014)
Y. Hori, in In Modern aspects of electrochemistry, ed. by C. Vayenas, R. White, M. Gamboa-Aldeco. Electrochemical CO2 reduction on metal electrodes (Springer, New York, 2008), pp. 89–189
J.H. Montoya, C. Shi, K. Chan, J.K. Nørskov, Theoretical insights into a CO dimerization mechanism in CO2 electroreduction. J. Phys. Chem. Lett. 6, 2032–2037 (2015)
J. Wu, M. Saito, M. Takeuchi, T. Watanabe, The stability of Cu/ZnO-based catalysts in methanol synthesis from a CO2-rich feed and from a CO-rich feed. Appl. Catal. A-Gen. 218, 235–240 (2001)
M.D. Segall, J.D.L. Philip, M.J. Probert, C.J. Pickard, P.J. Hasnip, S.J. Clark, M.C. Payne, First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys. Condens. Mat. 14, 2717 (2002)
J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996)
D. Vanderbilt, Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys. Rev. B 41, 7892–7895 (1990)
V.G. Ruiz, W. Liu, E. Zojer, M. Scheffler, A. Tkatchenko, Density-functional theory with screened van der Waals interactions for the modeling of hybrid inorganic-organic systems. Phys. Rev. Lett. 108, 146103 (2012)
J. Wellendorff, T.L. Silbaugh, D. Garcia-Pintos, J.K. Nørskov, T. Bligaard, F. Studt, C.T. Campbell, A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals. Surf. Sci. 640, 36–44 (2015)
A. Tkatchenko, L. Romaner, O.T. Hofmann, E. Zojer, C. Ambrosch-Draxl, M. Scheffler, Van der Waals interactions between organic adsorbates and at organic/inorganic interfaces. MRS Bull. 35, 435–442 (2011)
S.P. Liu, M. Zhao, W. Gao, Q. Jiang, Mechanistic insights into the unique role of copper in CO2 electroreduction reactions. ChemSusChem 10, 387–393 (2017)
N. Govind, M. Petersen, G. Fitzgerald, D. King-Smith, J. Andzelm, A generalized synchronous transit method for transition state location. Comput. Mater. Sci. 28, 250–258 (2003)
D. Donadio, L.M. Ghiringhelli, L. Delle Site, Autocatalytic and cooperatively stabilized dissociation of water on a stepped platinum surface. J. Am. Chem. Soc. 134, 19217–19222 (2012)
B.J. Hinch, L.H. Dubois, First-order corrections in modulated molecular beam desorption experiments. Chem. Phys. Lett. 171, 131–135 (1990)
X.-K. Gu, W.-X. Li, First-principles study on the origin of the different selectivities for methanol steam reforming on Cu(111) and Pd(111). J. Phys. Chem. C 114, 21539–21547 (2010)
J.B. Hansen, P.E. Højlund Nielsen, Methanol synthesis, in: handbook of heterogeneous catalysis, (Wiley-VCH Verlag GmbH & Co. KGaA, 2008)
A.A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, J.K. Norskov, How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 3, 1311–1315 (2010)
Acknowledgements
The authors acknowledge support from the Deutsche Forschungsgemeinschaft (DFG) through the grant proposal (JA1072/9-1 and 9-2), which was part of the research unit DFG-FOR1376. Further, support by the Program for Thousand Young Talents Plan and the National Natural Science Foundation of China (No. 21673095, 51631004), the computing resources of High Performance Computing Center of Jilin University, and National Supercomputing Center in Jinan and in Shenzhen China are acknowledged. Finally, the authors also acknowledge the computer time supported by the state of Baden-Württemberg through the bwHPC project and the DFG through grant number INST40/467-1 FUGG.
Author information
Authors and Affiliations
Corresponding authors
Electronic Supplementary Material
ESM 1
(DOCX 786 kb).
Rights and permissions
About this article
Cite this article
Liu, S.P., Zhao, M., Gao, W. et al. Theoretical Studies on the CO2 Reduction to CH3OH on Cu(211). Electrocatalysis 8, 647–656 (2017). https://doi.org/10.1007/s12678-017-0403-9
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12678-017-0403-9